Stabilization of oleaginous materials



Patented Feb. 22, 1949 STABELEZA'EHGN F OLEAGINUUS IVMi'EERHALS Frank A.Norris, Minneapolis, Minn, assignor to General Miiis, line, acorporation of Delaware No Drawing. Application December 1, 19%, SerialNo. 566.2%

18 (Ciairns. i

The present invention relates to a process of stabilizing oleaginousmaterials against the development of rancidity, and to the resultantproduct. rhe invention is directed particularly to oleaginous materialscomposed of or containing animal fats or oils, such as oils, shortening,salad dressings, spreads, and the like,

The present invention involves a synergistic anti-oxidant effectresulting from the combined use of a plurality of substances. It hasbeen found that combinations of certain antioxidants produce a resultantstability far in excess of the sum of the stabilities obtained by theuse of the compounds singly. i

It is therefore a primary object of the present invention to provide aprocess of stabilizing fatty or oleaginous materials against oxidationand the development of rancldity.

It is another object of the invention to provide products containingfats or oils which are stabilized against oxidation and the developmentoi rancidity.

A further object of the invention is to provide a process of stabilizingfatty or oleaginous products of animal origin by means of antioxidantswhich exhibit synergistic effects.

These and other objects of the invention will be apparent from thefollowing description of the invention with particular reference tospecific examples which are to be understood as illustrative only andnot as limiting the invention.

It has been found that a synergistic antioxidant effect is obtained bythe conjoint use of galllc acid and compounds containing the ene-dioigroup (HO-(i=(3-0n) such as l-a-scorbic acid. While ascorbic acid, whichis water-soluble, has been known to have antioxidant effect in aqueousmedia, it has not been particularly effective in fats probably becauseof its extremely low solubility. Gallic acid on the other hand has aconsiderable antioxidant etlect in fatty media. It has been found,however, that when these two compounds are used together, they exhibit apronounced synergistic efl'ect which gives the oleaginous material astability far in excess of that of the untreated material andjar inexcess of the sum of the individual stabilities contributed when each orthese cbm- 2 pounds is used alone. This is demonstrated by theiollowingtable showing the effect on prime steam lard.

Table I Swl Protective Sampliigggg Factor 1 Prime stoum Iard 3. 5 2(l)+0.02% gullic acid 107 30. 6 3 Prime steam lord... 2.5 l 4 (3)+0.05%l-ascorhic ll. 5 l G 5 Prime steam lard 3.8 6 (5) +0.02% gallicmidi-0.05% l-ascorbic acid 207. 5 5i. 7

In place of l-ascorbic acid other compounds havsynergistic action ofthese compounds is demonstrated by the following table showing theeffectiveness of gallic acid, l-ascorbic acid. and pamino-benzoic acid.

Table 1! "Swift" Pl'OtGCLlYl' Sample stnaglllligy Fucmrs 1 Prime steamlord 3.5 2 (l)+0.02% gallic acid 107 3|), l; 3 Prime steam lard 2.5 4(3)+0.05% l-oscorbic acid-loss than... ll. 5 4. G 5 Prime stcnm lard 3.8l l 6 (5) +0.02% galiic ncki +0.05% i-ascorbic acid 207.5 A. 7 7(3)+0.03% p-amino-bonzoic acid-loss than 2 3 i 8 (l)+0.05% l-ascorhicnclrl+0.0i% pnminobcnzoic acid.. 22 I (i. 7 9 (1)+0.05% l-ascorbicocid+0.03% n- I amino-bonzolc acid+0.02% izallic 5 acid 318 1 to. 9

The prime steam lard employed was the article the amount of antioxidantadded.

Instead of the amounts of antioxidants shown above, it is possible toemploy decidedly lower. concentration where such a high stability is notcent of each of a compound containing an enediol group, and a compoundselected from the group consisting of gallic acid and its loweraliphatic esters.

3. A process 01 stabilizing an oleaginous material of animal originwhich comprises incorporating therein, not substantially in excess oi'one-tenth per cent of each of l-ascorbic acid,

and a compound selected from the group consisting of gallic acid and itslower aliphatic esters.

4. A process oi stabilizing an oleaginous material oi animal originwhich comprises incorporating therein, not substantially in excess oione-tenth per cent of each or l-ascorbic acid and gallic acid.

necessary or desirable. The lower limit of antirial of animal originwhich comprises incorporatoxidant to be added appears to be dictated bythe resultant stability desired. There does not ap-.

pear to be any upper limit to the amount of antioxidant which may beemployed. However, the cost of the antioxidant constituents usuallydictates that they should not be employed in much greater concentrationthan 0.1 percent.

In addition to its effect on the antioxidant.

properties or the product, p-amino-benzoic acid has decided preservativeaction and represses microbiological growth. The common materialsemployed to inhibit oxidative rancidity have no effect onmicrobiological growth. Consequently yeast, molds, and the like,continue to grow and produce hydrolytic or other enzymic changes whichresult in rancidity. Thus, while the rancidity so .produced is adistinct disadvantage in itself, the presence of large numbers of microorganisms is an even greater disadvantage in view of the possible illeffect on those who consume such a product.

It is apparent that these various objections of the prior art areovercome by the present inven- 5. A process of stabilizing an oleaginousmateing therein, not substantially in excess of .1 per cent of each of acompound containing an enediol group, and a compound selected from thegroup consisting of gallic acid and its lower aliphatic esters.

6. A composition of matter comprising an oleaginous material of animaloringin containing, and being stabilized against the development ofrancidity by, not substantially in excess of onetenth per cent of eachof l-ascorbic acid, p-aminobenzoic acid, and gallic acid.

7. A" composition of matter comprising an oleaginous material of animalorigin containing, and being stabilized against the development ofrancidity by, not substantially in excess of .1 per cent oi. each of acompound containing an enediol group. D-amino-benzoic acid, and acompound selected from the group consisting of gallic acid and its loweraliphatic esters.

8. A process of stabilizing an oleaginous mation in that it inhibitsibOth oxidative rancidity and microbiological growth. Hydrolytic andenzymic rancidity are likewise inhibited in view of the inhibition ofmicrobological growth. Moreover all of the substances are non-toxic andthe p-amino-benzoic acid and l-ascorbic acid are recognlzed vitaminswhich perform additional functions when consumed.

While particular reference has been made to the use of l-ascorbic acidas a compound of the ene-diol group in the multiple synergy, it is to 7be understood that other compounds having this group, such as thosespecifically enumerated with respect to the single synergy, may also beemployed in the multiple synergy. Likewise the lower aliphatic esters ofgallic acid previously mentioned may be used in place of free gallicacid in the multiple synergy.

'-It is also to be understood that the invention may be applied toanimal oils or fats or any nature whether edible or not, all of whichproducts are contemplated by the term "oleaginous material of animalorigin as used in the appended claims.

I claim as my invention:

1. A composition of matter comprising an oleaginous material of animalorigin containing, and being stabilized against the development ofrancidity by, not substantially in excess of onetenth per cent of eachof l-ascorbic acid and gallic acid.

2. A composition of matter comprising an oleaginous material of animalorigin containing, and being stabilized against the development ofrancidity by, not substantially in excess of .1 per porating therein,not substantially in excess of one-tenth per cent of each of l-ascorbicacid, p-amino-benzoic acid,'and a compound selected from the groupconsisting of gallic acid and its lower aliphatic esters.

9. A process of stabilizing an oleaginous material of animal originwhich comprises incorporating therein, not substantially in excess 01'one-tenth per cent of each of l-ascorbic acid, p-amino-benzoic acid, andgallic acid.,

10. A process of stabilizing an oleaginous material of animal originwhich comprises incorporating therein, not substantially in excess of .1per cent of each of a compound containing an ene-diol group,p-amino-benzoic acid, and a compound selected from the group consistingof gallic acid and its lower aliphatic esters.

11. An edible shortening containing an oleaginous material of animalorigin, and being stabilized against the development of' rancidity by,not substantially in excess of .1 per cent of each of l-ascorbic acidand a compound selected from the group consisting of gallic acid and itslower aliphatic esters.

12. An edible shortening containing an oleaginous material oi animalorigin, and being stabilized against'the development 01' rancidity by,not substantially in excess oi .1 per cent of each of l-ascorbic acid,p-amino-benzoic acid, and a compound selected from the group consistingof gallic acid and its lower aliphatic esters.

13. A composition of matter comprising an oleaginous material of animalorigin containing, and being stabilized against the development of acidand its lower aliphatic esters and 0.05% of a compound containg anene-diol group.

14. A composition of matter comprising an oleaginous material of animalorigin containing. and being stabilized against the development ofrancidity by, approximately 0.02% of a compound selected from the groupconsisting of gallic acid and its lower aliphatic esters, 0.05% of acompound containing an ene-diol group, and 0.03% p-amino-benzoic acid.

15. A composition of matter comprising an oleaginous material of animalorigin containing, and being stabilized against the development ofrancidity by, approximately 0.02% gallic acid and 0.05% l-ascorbic acid.

16. A composition of matter comprising an oleaginous material of animalorigin containing, and being stabilized against the development ofrancidity by, approximately 0.02% gallic acid, 0.05% l-ascorbic acid,and 0.03% p-aminobenzoic acid.

17. A process of stabilizing an oleaginous material of animal originwhich porating therein approximately 0.02% of a compound selected fromthe group consisting of gallic acid and its lower aliphatic esters, and0.05% of a compound containing an ene-diol group.

comprises incor- 18. A process of stabilizing an oleagin'ous ma.- terialor animal origin which comprises incorporating therein approximately0.02% of a' compound selected from the group consisting of gallic. acidand its lower aliphatic esters, 0.05% of a compound containing anene-diol group, and

The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,763,326 Reed June 10, 19301,970,339 Rogers et a1 Aug. 14, 1934 1,975,755 Hoyt et a1. Oct. 2, 19342,159,986 Gray et a1 May 30, 1939 2,255,191 Sabalitschka et al. Sept. 9,1941 2,279,973 ,Dietrich Apr. 14, 1942 OTHER REFERENCES Filer et. al.,"Antioxidant L'osses During the Induction Period of Fat Oxidation," Oiland Soap," Oct. 1944, pages 289 to 292.

